The Effectiveness of Rice Husk Biochar Application to Metsulfuron

Methyl Persistence

Subhan Arridho, Saripah Ulpah and Tengku Edy Sabli

Department of Agrotechnology, Universitas Islam Riau, Pekanbaru, Indonesia

Keywords:

Herbicide, Metsulfuron Methyl, Persistence, Leaching, Rice Husk Biochar.

Abstract:

Metsulfuron methyl is an herbicide which has low toxicity and rapidly degraded in the soil, however DuPont

stated that it is very poisonous to aquatic organism. Rice husk biochar is commonly used as ameliorants,

moreoverit has ability to absorb and degradeharmful chemicals. This study aimed at investigating the

effectiveness of rice husk biochar application towards the persistence of metsulfuronmethyl in soil and seepage

water. This study applied completely randomized design factorial with two levels of herbicide dose (0 and 300

gr/ha) and four levels of percentage of rice husk biochar(0%, 5%, 10% and 15% of total soil). The results of

this research revealed that there was no metsulfuron methyl residue in soil of all treatments after 28 days of

herbicide treatment. The residue was found in seepageas much as 7.7 µg/L in treatment of 0% husk biochar

and 6.8 µg/L in treatment of 5%husk biochar. The seepage reduced by the increasing of the percentage of rice

husk biochar application. Thus, it can be concluded that giving the rice husk biochar is effective for absorbing

metsulfuron methyl and preventing it from leaching. However, itcould not hold the presence of metsulfuron

methyl longer in soil.

1 INTRODUCTION

Metsulfuron methyl is an herbicide active substance

which has low toxicity (LD50 in mice > 5000 mg/

kg), a low recommended dosage, and is also rapidly

degraded in the soil. Devlin et al. (1992) reported

thatmetsulfuron methyl, known as Ally, contains

DT50 for 2-4 weeks. However, in the DuPont Safety

Data Sheet, it is explained that Ally 20 WG(20%

metsulfuron methyl) is very poisonous to aquatic

organisms; it can cause long-term adverse effects in

the aquatic environment.

Persistence is the ability of the herbicide to

remain on the ground in an active state. The longer

the persistence of herbicides in the soil, the more

beneﬁcial it will be, in terms of efﬁcacy. However,

from an ecological perspective which is related

to environmental quality, the too-long persistence

of herbicides is certainly undesirable and should

be avoided because it will pollute the surrounding

environment. The persistence of herbicides in

the soil is inﬂuenced by several factors including:

volatilization, photodecomposition, adsorption,

leaching, microbial decomposition, chemical

decomposition, and uptake by plants (Rao, 2000).

Meanwhile, Jansar and Sahid (2016) stated that the

level of metsulfuronmethyl residue in the river near

oil palm plantations signiﬁcantly increased during

the rainy season because of leaching.

Rice husk biochar is commonly used as

ameliorants in agricultural cultivation to improve

soil quality by improving the physical, chemical and

biological properties of the soil. In addition, rice

husk biochar is also known to have the ability to

absorb agricultural chemicals and it is decomposed

in physically, chemically and biologically into

compounds that are not harmful for the environment.

Jing et al. (2018) assert that giving rice husk

biochar could reduce the loss of ethyl phenoxaprop

herbicides in the soil, and decreased the toxic effects

to earthworms. Moreover, Sudirja et al. (2015) stated

that the adsorption of paraquat herbicides by soil

increases in line with the increasing doses of zeolite,

straw, and activated charcoal in the soil.

This research was conducted to investigate the

effectiveness of giving rice husk biochar ameliorant

towards the persistence of metsulfuron methyl in soil

and seepage water.

Arridho, S., Ulpah, S. and Sabli, T.

The Effectiveness of Rice Husk Biochar Application to Metsulfuron Methyl Persistence.

DOI: 10.5220/0009119600800084

In Proceedings of the Second International Conference on Science, Engineering and Technology (ICoSET 2019), pages 80-84

ISBN: 978-989-758-463-3

2 MATERIAL AND METHODS

2.1 Materials

The The materials applied in this research include:

Ally 20 WG herbicide, top soil, rice husk biochar,

98% puriﬁed metsulfuron methyl solution (brand:

Sigma Aldrich), methanol gred HPLC, acetonitrile,

acetic acid, KH

, NaHCO

, HCl, and distilled

water.

The tools include: plastic pots,

Krisbow-semiautomatic handsprayers, scales,

Agilent 1220 Inﬁnity LC HPLC-VWD,

OpenlabChemstation Software, Gyrozen

centrifugation machines, hot plate stirrers

Thermolyne, orbital shaker Protech, Sartorius

analytic scales, Sartorius pH meters, ultrasonic

machines, Biotage ISL Isolate Env+ Solid Phase

Extraction (SPE) cartridge, manifold vacuum,

vacuum pump, syringe, 0.2 micron syringe ﬁlter,

analysis vial bottle, beaker glass, volumetric ﬂask,

centrifuge tube, ﬂask, measuring tube, glass bottle 20

ml, and micropipette.

2.2 Research Site and Methodology

This research was conducted in the green house of

the experimental garden at the Faculty of Agriculture,

Universitas Islam Riau. The extraction and residual

analysis of the active substance of metsulfuron methyl

herbicide was executed in the pesticide analysis

laboratory of the Faculty of Science and Technology,

UniversitiKebangsaan Malaysia. The research was

conducted from April to June 2018. This research

applied a completely randomized design (CRD)

factorial pattern with two levels of herbicide dose (0

and 300 gr/ha) and four levels of percentage of rice

husk biochar ameliorant (0%, 5%, 10% and 15% of

total soil). The total amount of soil and rice husk

biochar in the pot is 2 kg, which was mixed evenly

(Figure 1). The treatment was repeated 3 times, so

that there were 24 units of the total experimental

treatments.

Herbicide was sprayed onto the ground with a

concentration of herbicide application 0.67 gr/L of

water and a spray volume of 450 l/ha. Each pot

was watered with 200 ml of water after 17 days of

herbicide application daily. The water that seeped out

under the pot was collected to be analyzed.

2.3 Sampling

The soil with the same treatment was composited,

stirred evenly, aerated for 2 hours then taken as much

Figure 1: Mixture of soil and rice husk biochar.

as 500 grams per treatment. Meanwhile, seeped out

water from pots that have been collected each day

was taken as the sample for as much as ± 250 ml per

treatment and it was put in a glass bottle.

2.4 Metsulfuron Methyl Extraction

For the extraction of metsulfuron methyl in the soil,

5 grams of soil sample were prepared, then mixed

with 0.1 M NaHCO

. The samples were shaken with

orbital shaker (200 rpm, 2 hours). After that, they

were centrifuged for 20 minutes at 4000 rpm. The

SPE cartridge was rinsed with 3 ml of acetonitrile

and 3 ml of distilled water. The supernatant resulted

was ﬂowed about 2-3 ml per minute through the

SPE cartridge (Figure 2). Then, metsulfuron methyl

absorbed in the SPE cartridge was separated with

methanol and stored in a 20 ml glass bottle. The

extraction results were dried to a range of 1 ml. After

that, it was sucked with a syringe equipped with a 0.2

micron ﬁlter, then transferred to a 1.5 ml analysis vial

bottle.

Figure 2: Soil supernatant was ﬂowed through SPE

cartridge for absorbingmetsulfuron methyl.

For the extraction of metsulfuron methyl in

seepage, 250 ml of seepage water samples were

prepared in a glass bottle. The pH of the water sample

was adjusted between 5-6 with potassium hydroxide

and or hydrochloric acid. The cartridge was rinsed

The Effectiveness of Rice Husk Biochar Application to Metsulfuron Methyl Persistence

with 3 ml of acetonitrile and 3 ml of distilled water.

Then, the water sample was ﬂowed about 2-3 ml

per minute through the SPE cartridge. Next, the

metsulfuron methyl that was absorbed in the SPE

cartridge was separated with methanol and stored in

a 20 ml glass bottle. The extraction results were

dried to a range of 1 ml. After that, it was sucked

with a syringe equipped with a 0.2 micron ﬁlter, then

transferred to a 1.5 ml analysis vial bottle.

2.5 Metsulfuron Methyl Analysis

To provide a standard metsulfuron methyl primary

solution, 1.02 mg metsulfuron methyl (98% purity)

was weighed and dissolved with 50 ml of methanol

gred HPLC to produce a solution with a concentration

of 20 mg/L. Then, it was diluted so that the

concentration became 10 mg/L.

Next, to produce a standard metsulfuron methyl

curve, 5 series of secondary solutions were

formulated with concentrations of 50 µg/L, 100

µg/L, 200 µg/L, 300 µg/L and 500 µg/L respectively.

A secondary solution was formulated by dissolving

the primary solution as much as 0.05 ml, 0.1 ml,

0.2 ml, 0.3 ml, and 0.5 ml with methanol gred

HPLC until the solution volume became 10 ml in a

volumetric ﬂask. All the solutions made were placed

in an ultrasonic device for 20 minutes and then

injected into a 1.5 ml vial analysis bottle by ﬁltering

it using 0.2 micron ﬁlters to be analyzed using HPLC.

Furthermore, the standard solution of metsulfuron

methyl, methanol, soil samples and water samples

stored in 1.5 ml vial bottle was inserted into the

Agilent 1220 Inﬁnity LC HPLC. Samples of each vial

bottle were automatically analyzed for 18 minutes and

the results of the analysis were displayed through the

OpenlabChemstation interface on a computer screen.

3 RESULTS AND DISCUSSION

3.1 Calibration Curve

The highest correlation was obtained from a

combination of 3 series of metsulfuronmethyl

standard solutions, namely 100 g/L, 200 µg/L, and

300 µg/L, which had a correlation coefﬁcient of

0.995. This implies that the concentration of standard

solutions gives an effect of 99% on the response

of the instrument, while the rest is inﬂuenced by

other variables.The above curve also shows that

metsulfuron methyl can be detected in the range of

RT (retention time) 5,391 minutes (Figure 3).

Figure 3: Linear regression curve of standard metsulfuron

methyl solution.

3.2 The Persistence of Metsulfuron

Methyl in Soil

Table 1 demonstrates that the metsulfuron methyl

residue was not found on the soil during HPLC

analysis. The ameliorant treatment of rice husk

biocharrevealed the same effect as the one without the

treatment of husk biochar after 28 days of herbicide

application. In other words, this research found that

rice husk biochar could not maintain the persistence

of metsulfuron methyl longer in the soil.

Table 1: Level of metsulfuron methyl residues in soiln

Treatment

Metsulfuron Methyl

Ret

Time

(minute)

Area

(mAU*s)

Residual

Level

(µg/L)

0% husk

biochar

5.391 0 0

5% husk

biochar

5.391 0 0

10%

husk

biochar

5.391 0 0

15%

husk

biochar

5.391 0 0

One of the important processes that control the

behavior of herbicides in the soil is the adsorption

carried out by the soil components. Herbicides can

be found in soil in the form of dissolved molecules

of the liquid phase and/or molecules that are bound

to soil phases such as minerals, organic matter, plant

residues, etc. (Zanini et al., 2008). In addition,

more than 36.3% to 55.7% of the applied metsulfuron

methyl turns into a residual form that binds to the soil

(Pons and Baniuso, 1998; Xu et al., 2002; Wang et

al., 2002). However, how the mechanism of colloidal

soil holds metsulfuron methyl and its metabolites is

still not clearly conﬁrmed. Possible bonds between

herbicides and colloidal soils include: (1) ionic bonds,

ICoSET 2019 - The Second International Conference on Science, Engineering and Technology

(2) hydrogen bonds, (3) van der waals forces, (4)

ligand exchanges, (5) charge transfer complexes, (6)

hydrophobic partitioning, (7) covalent bonds and (8)

sequestration (Gevao et al., 2000).

Based on the results of this research, the

degradation of metsulfuron methyl herbicide in the

soil is resulted from through several degradation

processes, namely: hydrolysis, photolysis and

microbial decomposition. However, the authors

assume that the degradation of metsulfuron methyl

was more inﬂuenced by chemical degradation

(hydrolysis) than by biochemistry (microorganisms)

or physics (photolysis). This is in accordance with

Devlin et. al. (1992) who reported that the

degradation of sulfonylurea herbicides, such as Ally

Classic and Glean, is mostly caused by hydrolysis.

It is supported by a research conducted by Manna

(2015), which reported that the main mechanism of

chemical degradation of sulfonylurea herbicides is

caused by hydrolysis.

3.3 The Levels of Methyl Metsulfuron

Residue in Seepage

Based on the results of HPLC analysis, it was found

that the residual level of metsulfuron methyl in

seepage was 7.7 µg/L in the treatment of 0% husk

biochar and 6.8 µg/L in the treatment of 5% husk

biochar. Whereas, there was no metsulfuron methyl

residue was found in seepage at 10% husk biochar

and 15% husk biochar(table 2). This shows that the

level of residual metsulfuron methyl in seepage water

tends to decrease with the increasing amount of rice

husk biochar applied.

Table 2: Level of metsulfuron methyl residues in seepage

water

Treatment

Metsulfuron Methyl

Ret

Time

(minute)

Area

(mAU*s)

Residual

Level

(µg/L)

0% husk

biochar

5.365 1745.06 7.68

5% husk

biochar

5.357 1533.71 6.75

10%

husk

biochar

5.391 0 0

15%

husk

biochar

5.391 0 0

The authors believe that this tendency occured

due to the adsorption by rice husk biochar applied

in the soil, preventingmetsulfuron methyl from being

leached. Hence, it can be concluded that the addition

of rice husk biochar in this research is very effective

to prevent metsulfuron methyl from leaching. As a

result, it can reduce the negative impacts that arise in

the water ecosystem around it.

This research ﬁnding is in accordance with that

of by Zhelezova et al. (2017) who reported that

adding wood charcoal to sandy and clay soils cause

the adsorption of diuron herbicides increased. The

increasing of diuron adsorption in line with the

addition of charcoal, because charcoal has many

absorbent surfaces that can bind non-polar herbicides

so it can reduce the risk of leaching. Jing et al. (2018)

investigated that the addition of rice husk biochar

could slow the loss of ethyl phenoxaprop herbicide

in the soil.

The prevention of metsulfuron methyl leaching

can certainly be used as a solution to prevent

the contamination of active substance of herbicides

reaching to underground water and other water

ecosystems such as rivers and lakes.

A very low residual level of metsulfuron

methyl does not mean have no negative impact

on the environment. Fairchild (1995) reported

that metsulfuron methyl could cause the reduction

of 50% of the number of Lemna minor leaves

in a period of 14 days with an EC50 0.4

µg/L. If it accumulates continuously over a long

period of time, it is not impossible that other

aquatic organisms can be affected, including:

algae (Selenastrumcapricornutum, EbC

3.9 mg/L),

crustaceans (Daphnia magna, EC

> 150 mg/L), and

ﬁsh (Bluegill sunﬁsh, LC

> 150 mg/L).

4 CONCLUSIONS

Metsulfuron methyl was completely degraded 28 days

after herbicide application regardless the application

of rice huskbiochar, which is assumed to be caused

by hydrolysis as the main factor.

The residual metsulfuron methyl was found in

seepage water in the treatment of 0% husk biocharas

much as 7.7 µg/L and in the treatment of 5% husk

biochar as much as 6.8 µg/L, while the treatment of

10% and 15% husk biochar was 0 µg/L. This indicates

that the addition of rice husk charcoal ameliorant

is very effective in absorbing and breaking down

metsulfuron methyl in the soil, so that the further

contamination of herbicide metsulfuron methyl into

the surrounding water environment can be avoided.

The Effectiveness of Rice Husk Biochar Application to Metsulfuron Methyl Persistence

ACKNOWLEDGMENTS

The authors wish to thank Universitas Islam Riau

for funding this publication and Centre for Earth

Sciences and Environment, Faculty of Science and

Technology, Universiti Kebangsaan Malaysia for

providing technical guidance and research fasilities.

REFERENCES

Devlin, D. L., Peterson, D. E., and Regehr, D. L. 1992.

Residual Herbicides, Degradation and Recropping

Interval.

Fairchild, J. F., Ruessier, D. S., Lovely, P. A., Whites,

D. A., and Heine, P. R. 1995. An Aquatic

Plant Risk Assessment of Sixteen Herbicides Using

Toxicity Tests with Selenastrumcapricornutum and

Lemna minor.

Gevao, B., Semple, K. T., and Jones, K. C. 2000. Bound

Pesticide Residue in Soils: A review. Environmental

Pollution, 108:3–14.

Jansar, K. M. and Sahid, I. B. (20). 2016. Residue

Determination and Monitoring of The Levels of

Metsulfuron Methyl in Selected Rivers at TasikChini

Pahang Malaysia. Malaysian Journal of Analytical

Sciences 20.

Jing, X., Wang, T., Yang, J., Wang, Y., and Xu, H.

2018. Effect of Biochar on The Fate and Toxicity of

Herbicide Fenoxaprop-Ethyl in Soil. R. Soc. Open Sci,

5:171875.

Pons, N. and Baniuso, E. 1998. Fate of metsulfuron-methyl

in soils in relation to pedo-climatic conditions. Pestic.

Sci, 53:311–323.

PT. (20). DuPont Agricultural Products Indonesia. Lembar

Data Keselamatan Ally 20 WDG.

Rao, V. S. (2000). Principle of Weed Science 2nd Eds.

Science Publisher, Inc.

S., M. (2015). Effect of Biochar Amendments on Fate of

Pyrazosulfuron-Ethyl in Soil.

Sudirja, R., Ariﬁn, M., and Joy, B. 2015.

AdsorpsiParaquatdanSifat Tanah padaTigaSubgrup

Tanah AkibatPemberianAmelioran.

JurnalAgrikultura, 26.

Wang, H. Z., Xu, J. M., Xie, Z. M., and Ye, Q. F. 2002.

Dynamics of bound residues of metsulfuron-methyl in

soil humus. Acta Sci. Curcum. 22, 22.

Xu, J. M., Wang, H. Z., Xie, Z. M., and Chen, Z. L. 2002.

Distribution of bound residues of metsulfuron-methyl

in soil combined humus. China Environ. Sci. 22, 22.

Zanini, G. P., Maneiro, C., Waiman, C., Galantini, J. A., and

Rosell, R. A. 2009. Adsorption of Metsulfuron Methyl

on Soils under No-Till System in Semiarid Pampean

Region, Argentina. Geoderma, 149:110–115.

Zhelezova, A., Cederlund, H., and Stenstrom, J. 2017.

Effect of Biochar Amendment and Ageing on

Adsorption and Degradation of Two Herbicides.

Water Air Soil Pollut, 228:216.

ICoSET 2019 - The Second International Conference on Science, Engineering and Technology